A alfafa (Medicago sativa L.) é uma forrageira leguminosa com alto potencial produtivo, qualidade de forragem e variabilidade de utilização. Quando bem manejada, é uma cultura capaz de fornecer forragem de qualidade e promover um aumento na produtividade dos rebanhos. Para se expandir o uso desta forrageira no país, torna-se necessário superar alguns entraves, como a falta de cultivares adaptadas as diferentes condições edafoclimáticas e resistência ao pastejo. Este trabalho busca avaliar o efeito de diferentes doses de calcário combinadas a distintas formas de aplicação sobre o desenvolvimento da cultura da alfafa em sistema plantio direto. O experimento foi conduzido na Estação Experimental do Instituto Agronômico do Paraná, localizada no Município de Pato Branco - PR. A cultivar utilizada foi a Crioula. O delineamento experimental foi o de blocos ao acaso com quatro repetições em parcelas sub-sub divididas. Para as avaliações dos atributos químicos do solo as parcelas constituíram-se das formas de aplicação de calcário (aração+gradagem, subsolagem e superficial), as sub-parcelas pelas doses de calcário (0, 2, 4, 6 e 8 t. ha-1) e as sub-sub parcelas pelas profundidades de solo amostradas (0-5; 5-10; 10-20 e 20-30 cm). Para a avaliação dos teores de N, P, K, Ca e Mg do tecido foliar da alfafa e taxa de acúmulo de MS diária as parcelas constituíram-se pelos dias acumulados (56, 116, 144, 184, 220, 248, 286, 322, 353, 391, 432, 485, 530, 574 e 597 dias), as sub-parcelas pelas formas de aplicação de calcário (aração+gradagem, subsolagem e superficial) e as sub-sub parcelas pelas doses de calcário (0, 2, 4, 6 e 8 t. ha-1). A aplicação de calcário, mesmo que de forma superficial, provocou aumentos de pH, dos teores de Ca e Mg e da saturação por bases do solo, bem como, causou a diminuição dos teores de Al e da acidez potencial do solo (H+Al), sendo estes efeitos percebidos nas camadas mais inferiores do solo. Apenas em um período de avaliação de taxa de acúmulo de matéria seca (220 dias acumulados) constatou-se influência da forma de aplicação de calcário, sendo que nas 14 demais avaliações, não se constatou efeito deste fator. Plantas cultivadas com 4 t. ha-1 de calcário nas parcelas sem incorporação apresentaram teores de N do tecido foliar da alfafa superiores aos encontrados nas demais plantas onde o calcário foi incorporado. Não há inconveniência da aplicação do calcário na superfície do solo sobre os teores foliares de Ca, K, Mg e P para alfafa cultivada sob sistema de plantio direto. A prática de aração e gradagem ou de subsolagem visando à incorporação de calcário no sistema de plantio direto mostrou-se desnecessária. Em consequência disso, recomenda-se que, para a alfafa cultivada em sistema plantio direto estabilizado, a aplicação de calcário no solo seja feita de forma superficial. / Alfalfa (Medicago sativa L.) is a forage legume with high yield potential, forage quality and variability of use. When well managed, is a culture able to provide quality forage and promote an increase in productivity of the herds. To enlarge the use of this forage in the country, it is necessary to overcome some obstacles, such as lack of suitable cultivars in our different environmental conditions and resistance to grazing. This study sought to determine the effect of different doses of lime combined with different forms of application to the development of culture in the alfalfa no-till system. The experiment was conducted at the Experimental Station of the Agronomic Institute of Paraná, located in Pato Branco - PR. The cultivar used was Creole. The experimental design was a randomized block design with four replications in split sub-divided. For the evaluations of soil chemical attributes the plots consisted of the forms of lime application (plowing + harrowing, subsoil and surface), the sub-plots for limestone (0, 2, 4, 6 and 8 t. ha -1) and the sub-sub plots sampled for soil depths (0-5, 5-10, 10-20 and 20-30 cm). To assess the levels of N, P, K, Ca and Mg in alfalfa leaf tissue and accumulation rate of MS daily portions constituted by accumulated days (56, 116, 144, 184, 220, 248, 286, 322, 353, 391, 432, 485, 530, 574 and 597 days), the sub-plots in the forms of lime application (plowing + disking, sub soiling and surface) and the sub-sub plots for limestone (0, 2, 4, 6 and 8 tonnes. ha-1). Liming, even if superficially, caused increases in pH, Ca and Mg and base saturation of the soil and caused the decrease in the levels of Al and potential soil acidity (H + Al ), and these perceived effects in lower layers of soil. Only in an evaluation period of accumulation rate of dry matter (220 cumulative days) revealed the influence of lime application form, and the 14 other reviews, we found no effect of this factor. Plants grown with 4 t. ha-1 of lime in the plots without incorporation showed concentration of the alfalfa leaf tissue than those found in other plants where the limestone was incorporated. No inconvenience of applying lime to the soil surface on the leaf Ca, K, Mg and P for alfalfa grown under no-tillage system. The practice of plowing or disking and sub soiling seeking the incorporation of lime in the no-tillage system proved to be unnecessary. As a result, it is recommended that for alfalfa grown in no-till system stabilized, the application of lime in the soil is made lightly.

A alfafa (Medicago sativa L.) é uma forrageira leguminosa com alto potencial produtivo, qualidade de forragem e variabilidade de utilização. Quando bem manejada, é uma cultura capaz de fornecer forragem de qualidade e promover um aumento na produtividade dos rebanhos. Para se expandir o uso desta forrageira no país, torna-se necessário superar alguns entraves, como a falta de cultivares adaptadas as diferentes condições edafoclimáticas e resistência ao pastejo. Este trabalho busca avaliar o efeito de diferentes doses de calcário combinadas a distintas formas de aplicação sobre o desenvolvimento da cultura da alfafa em sistema plantio direto. O experimento foi conduzido na Estação Experimental do Instituto Agronômico do Paraná, localizada no Município de Pato Branco - PR. A cultivar utilizada foi a Crioula. O delineamento experimental foi o de blocos ao acaso com quatro repetições em parcelas sub-sub divididas. Para as avaliações dos atributos químicos do solo as parcelas constituíram-se das formas de aplicação de calcário (aração+gradagem, subsolagem e superficial), as sub-parcelas pelas doses de calcário (0, 2, 4, 6 e 8 t. ha-1) e as sub-sub parcelas pelas profundidades de solo amostradas (0-5; 5-10; 10-20 e 20-30 cm). Para a avaliação dos teores de N, P, K, Ca e Mg do tecido foliar da alfafa e taxa de acúmulo de MS diária as parcelas constituíram-se pelos dias acumulados (56, 116, 144, 184, 220, 248, 286, 322, 353, 391, 432, 485, 530, 574 e 597 dias), as sub-parcelas pelas formas de aplicação de calcário (aração+gradagem, subsolagem e superficial) e as sub-sub parcelas pelas doses de calcário (0, 2, 4, 6 e 8 t. ha-1). A aplicação de calcário, mesmo que de forma superficial, provocou aumentos de pH, dos teores de Ca e Mg e da saturação por bases do solo, bem como, causou a diminuição dos teores de Al e da acidez potencial do solo (H+Al), sendo estes efeitos percebidos nas camadas mais inferiores do solo. Apenas em um período de avaliação de taxa de acúmulo de matéria seca (220 dias acumulados) constatou-se influência da forma de aplicação de calcário, sendo que nas 14 demais avaliações, não se constatou efeito deste fator. Plantas cultivadas com 4 t. ha-1 de calcário nas parcelas sem incorporação apresentaram teores de N do tecido foliar da alfafa superiores aos encontrados nas demais plantas onde o calcário foi incorporado. Não há inconveniência da aplicação do calcário na superfície do solo sobre os teores foliares de Ca, K, Mg e P para alfafa cultivada sob sistema de plantio direto. A prática de aração e gradagem ou de subsolagem visando à incorporação de calcário no sistema de plantio direto mostrou-se desnecessária. Em consequência disso, recomenda-se que, para a alfafa cultivada em sistema plantio direto estabilizado, a aplicação de calcário no solo seja feita de forma superficial. / Alfalfa (Medicago sativa L.) is a forage legume with high yield potential, forage quality and variability of use. When well managed, is a culture able to provide quality forage and promote an increase in productivity of the herds. To enlarge the use of this forage in the country, it is necessary to overcome some obstacles, such as lack of suitable cultivars in our different environmental conditions and resistance to grazing. This study sought to determine the effect of different doses of lime combined with different forms of application to the development of culture in the alfalfa no-till system. The experiment was conducted at the Experimental Station of the Agronomic Institute of Paraná, located in Pato Branco - PR. The cultivar used was Creole. The experimental design was a randomized block design with four replications in split sub-divided. For the evaluations of soil chemical attributes the plots consisted of the forms of lime application (plowing + harrowing, subsoil and surface), the sub-plots for limestone (0, 2, 4, 6 and 8 t. ha -1) and the sub-sub plots sampled for soil depths (0-5, 5-10, 10-20 and 20-30 cm). To assess the levels of N, P, K, Ca and Mg in alfalfa leaf tissue and accumulation rate of MS daily portions constituted by accumulated days (56, 116, 144, 184, 220, 248, 286, 322, 353, 391, 432, 485, 530, 574 and 597 days), the sub-plots in the forms of lime application (plowing + disking, sub soiling and surface) and the sub-sub plots for limestone (0, 2, 4, 6 and 8 tonnes. ha-1). Liming, even if superficially, caused increases in pH, Ca and Mg and base saturation of the soil and caused the decrease in the levels of Al and potential soil acidity (H + Al ), and these perceived effects in lower layers of soil. Only in an evaluation period of accumulation rate of dry matter (220 cumulative days) revealed the influence of lime application form, and the 14 other reviews, we found no effect of this factor. Plants grown with 4 t. ha-1 of lime in the plots without incorporation showed concentration of the alfalfa leaf tissue than those found in other plants where the limestone was incorporated. No inconvenience of applying lime to the soil surface on the leaf Ca, K, Mg and P for alfalfa grown under no-tillage system. The practice of plowing or disking and sub soiling seeking the incorporation of lime in the no-tillage system proved to be unnecessary. As a result, it is recommended that for alfalfa grown in no-till system stabilized, the application of lime in the soil is made lightly.

Três catalisadores contendo o mesmo teor de fase ativa (20% de óxido de molibdênio e 4% de óxido de níquel), mas constituídos por diferentes suportes (alumina, sílica-alumina e alumina zeólita) foram preparados com o objetivo de se obter catalisadores bifuncionais com acidez distinta e boa dispersão da fase metálica visando analisar o papel da acidez do suporte na conversão da tetralina. Os catalisadores e seus respectivos suportes foram caracterizados na formas óxido e sulfeto e avaliados na reação de hidrogenação da tetralina, que representa bem os monoaromáticos presentes nas correntes de petróleo. A caracterização textural mostrou que tanto a área específica quanto o volume de poros foram pouco alterados após a incorporação dos óxidos metálicos aos suportes. Os catalisadores apresentaram uma dispersão relativamente boa da fase ativa, conforme indicado pelos resultados de MET, DRX e DRS. Os resultados obtidos por TPD de n-propilamina e por espectroscopia de IV de piridina mostraram que a incorporação de óxidos de molibdênio e níquel levou a um aumento da acidez de Brönsted, o que foi atribuído à criação de novos sítios ácidos associados ao óxido de molibdênio ou a sítios de interface deste com o suporte. Obteve-se uma boa correlação entre a atividade de conversão da tetralina e o rendimento em produtos aromáticos e abertura de ciclo naftênico com a acidez de Brönsted do suporte, com a seguinte ordem de atividade para a conversão da tetralina: NiMo/alumina < NiMo/sílica-alumina < NiMo/alumina zeólita. O aumento do rendimento de produtos de hidrogenação foi relacionado à existência de um efeito eletrônico entre os sítios de Brönsted do suporte e as partículas de sulfeto suportado. No entanto, para o catalisador suportado em alumina-zeólita, onde em princípio a fase hidrogenante estaria distante dos sítios ácidos, sugeriu-se a possibilidade de uma rota alternativa de hidrogenação a partir do metil-indano formado nos centros ácidos da zeólita. / Three sulfided catalysts with the same active phase content (20 wt% of molybdenum oxide and 4 wt% of nickel oxide) and deposited on different supports (alumina, silica-alumina and alumina-Y zeolite) were prepared aiming to obtain bifunctional catalysts with different acidities and good dispersion of the sulfide phase for analyzing the role of the support acidity on the hydroconversion of tetraline. The supports and respective catalysts were characterized in the oxide and sulfide forms and were evaluated for the hydroconversion of tetraline, which is representative of the monoaromatic compounds present in the diesel fraction. The textural characterization indicated that the specific surface areas as well as the pore volumes were very little affected by the impregnation of the metal oxides in the supports. The catalysts presented a relatively good dispersion of the active phase as indicated by TEM, XRD and DRS results. Pyridine IR spectroscopy and n-propylamine TPD results showed an increase of Brönsted acidity after impregnation of molybdenum and nickel oxides, which were attributed to the creation of new acidic sites associated to the supported molybdenum oxide or to sites at the interface of this oxide with the support. A good correlation of the support Brönsted acidity with the overall conversion of tetraline was observed, as well as with the aromatic and ring opening product yields. The following activity ranking for tetraline conversion was observed: NiMo/alumina < NiMo/silica-alumina < NiMo/alumina-zeolite. An increase of the hydrogenation product yields with the support acidity was also observed which was ascribed to an electronic effect between the support acidic Brönsted sites and the sulfide particles. However, for alumina-zeolite supported catalyst, where acidic and hydrogenating sites are not in close vicinity, an alternative reaction route was proposed considering the hydrogenation of the methyl-indane formed by tetraline isomerization on the Brönsted sites.

Orientadores: Marcelo Menossi Teixeira, Renato Atílio Jorge / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-16T10:26:16Z (GMT). No. of bitstreams: 1 Mattiello_Lucia_D.pdf: 1855407 bytes, checksum: 309c252e258389c8f81e79e8fba49e74 (MD5) Previous issue date: 2010 / Resumo: A presença do alumínio (Al) em solos ácidos é o principal fator limitante da produtividade agrícola no Brasil e no mundo. A resposta desenvolvida pelas plantas contra o Al é complexa e a identificação de genes responsivos após a exposição ao íon através de técnicas de análise em larga escala, como microarrays, pode facilitar a sua compreensão. Este projeto possui como objetivo ampliar o conhecimento sobre a fisiologia e a regulação gênica de raízes e folhas utilizando genótipos contrastantes de milho (Cat100-6 (Al-tolerante) e S1587-17 (Al-sensível)) cultivadas em solo ácido com concentração fitotóxica de Al. As linhagens de milho Cat100-6 e S1587-17 foram cultivadas por um ou três dias em solo ácido (pH 4,1) ou solo corrigido com Ca(OH)2 (pH 5,5). O genótipo S1587-17 apresentou uma maior inibição do crescimento radicular, resultado este altamente correlacionado com a acumulação de Al nos ápices radiculares e deposição de calose. Os dados fisiológicos confirmam a discriminação entre as duas linhagens em solo, abrindo perspectivas para entender pela primeira vez a base molecular das alterações das plantas em condições próximas à realidade de campo. O transcriptoma de raízes possibilitou a identificação possíveis candidatos a tolerância ao Al. Adicionalmente, com um experimento de hidroponia separamos as variáveis pH e presença de Al, ambas condições diferenciais do tratamento com solo. Identificamos, entre os candidatos, genes responsivos pela presença do Al e não pela acidez delimitando assim os genes com possíveis papéis na tolerância ao Al presente no solo ácido a apenas três: retinol desidrogenase, um fator de transcrição WRKY e uma proteína desconhecida. Esses resultados permitem concluir que o cultivo em solo é diferencial em relação à hidroponia, e outros fatores que apenas presentes no substrato solo podem provocar a indução de alguns genes. Diversas vias metabólicas são afetadas na linhagem sensível pelo tratamento em solo ácido e podem estar envolvidas na inibição radicular como a produção de lignina, celulose e calose e a síntese de etileno e auxina. O mapeamento nos cromossomos dos genes identificados pelo experimento de microarray das raízes de milho permitiu a identificação de genes localizados dentro de QTLs de milho previamente descritos na literatura como responsáveis pelo fenótipo tolerante. Diante esse resultado, podemos especular o papel de genes como uma proteína ligadora de RNA, uma inibidora de proteases e ciclinas na tolerância ao Al contido no solo ácido. Pela primeira vez na literatura, o transcriptoma de folhas coletadas após três dias de cultivo em solo ácido ou solo corrigido foi obtido com o uso de microarrays da Affymetrix. Essa análise indicou profundas alterações na Cat100-6, em contraposição à ausência de alteração significativa nas folhas na S1587-17. Genes referentes à fotossíntese e a fotorrespiração foram regulados negativamente pelo tratamento em solo ácido no genótipo tolerante. Contudo, o ciclo do ácido cítrico está ativado indicando uma putativa participação da produção de ácidos orgânicos nas folhas na resposta ao Al / Abstract: The presence of aluminum (Al) is the main factor limiting crops yield in Brazil and worldwide. The plant responses developed against this ion are complex and the identification of responsive genes after exposure to the ion with the use of a large scale technique, such as microarrays, can facilitate its comprehension. This project aimed to amplify the knowledge about physiology and gene expression regulation of roots and leaves associated towards Al resistance using contrasting maize genotypes (Cat100-6 (Al-tolerant) and S1587-17 (Al-sensitive) cultivated in acid soil containing phytotoxic concentrations of Al. Maize lines Cat100-6 and S1587-17 were cultivated for one or three days in acid soil (pH 4,1) or limed soil with Ca(OH)2 (pH 5,5). The genotype S1587-17 presented a higher root growth inhibition, which is highly correlated with Al accumulation in the root apexes and callose deposition. The physiological data confirms the discrimination of the two maize lines cultivated in soil, opening perspective to understand for the first time the molecular bases of alterations in plants on a closer condition to the field. Transcriptome from roots made possible the identification of possible tolerance candidates and genes constitutively expressed genes in the tolerant line. Additionally, throw a hydroponic experiment we splited the variables pH and Al presence, both differential conditions between soil treatments. It was possible to identify, among the candidates, genes responsive in the presence of Al in acid soil rather than acidity limiting genes with a possible roles in Al present in the acid soil tolerance to only three: retinol dehydrogenase, the transcription factor WRKY and an unknown protein. These results allow the conclusion that the soil culture is different in relation to hydropony, and other factors present only in soil substrate could provoke the induction of some genes. Several metabolic pathways were affected in the sensitive line after acid soil growth and could be involved on root growth inhibition such as lignin, cellulose and callose production and ethylene and auxin synthesis. The mapping of the identified genes through the microarray experiments into the chromosomes allowed the identification of genes localized into maize QTLs previously reported in the literature as responsible for the tolerant phenotype. Facing these results, we can speculate the role of these genes such as a RNA binding protein, a protease inhibitor, and cyclines in the Al present in the acid soil tolerance. For the first time in literature, the transcriptome of leaves collected after three days in culture with acid soil or limed soil with the Affymetrix microarrays. This analysis indicated great alterations in Cat100-6, meanwhile S1587-17 showed no significative alteration. Genes related to photosynthesis and photorespiration were down-regulated due acid soil treatment in the tolerant genotype. However, citric acid cycle was activated indicating the putative partitipation of organic acids produced in the leaves in thr Al response / Doutorado / Genetica Vegetal e Melhoramento / Doutor em Genetica e Biologia Molecular

Orientadores: Heloise de Oliveira Pastore, Leonardo Marchese / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-16T13:00:02Z (GMT). No. of bitstreams: 1 Superti_GuilhermeBicaleto_D.pdf: 4945691 bytes, checksum: 95096830b37dc8f5ad0537d64a2481e7 (MD5) Previous issue date: 2009 / Resumo: Este trabalho descreve a síntese de dois materiais lamelares, um silicato, a magadiita, e um aluminofosfato, a AlPO-kanemita. No primeiro caso foi feita a substituição isomórfica com alumínio e no segundo com ferro ou vanádio e também se variou os tipos de alquilaminas no espaço interlamelar, alternandose cadeias longas e curtas. A magadiita foi convertida em sua forma ácida por dois métodos diferentes: um pela troca iônica com NH4+ e outro pela troca iônica com HCl. Estudos de DRX em temperaturas crescentes demonstraram que a estabilidade térmica da magadiita não se altera após a introdução de alumínio. A acidez dos materiais foi avaliada pelo monitoramento por FTIR do CO adsorvido e verificou-se que a introdução de alumínio produz sítios de alta acidez, comparável aos zeólitos. A comparação dos dois materiais ácidos diferentes indicou que os sítios produzidos por desamoniação são mais acessíveis ao CO do que os produzidos pela troca com HCl. A AlPO-kanemita foi utilizada na preparação de compósitos poliméricos por dois métodos diferentes, por mistura no estado fundido e polimerização in situ. No primeiro caso os polímeros usados, PP e EVA, não conseguem acessar o espaço interlamelar, enquanto que no segundo caso o PS e a PA6 tem acesso, mas este depende das aminas presentes no espaço interlamelar. As massas moleculares do PS não são afetadas pela presença da AlPO-kan, mas as da PA6 são drasticamente reduzidas. A introdução dos metais de transição tem efeito na decomposição térmica dos polímeros, produzindo uma maior quantidade de um material carbonáceo quando comparada aos análogos sem metal, o que diminui a inflamabilidade do material. / Abstract: This work describes the synthesis of two layered materials, magadiite and AlPOkanemite. The first is a silicate analogous to the natural hydrated layered silicate where isomorphous substitution with aluminum was performed. AlPO-kanemite is an aluminophosphate with the same structure as the hydrated layered silicate kanemite, from the same family as magadiita. It also passed by isomorphous substitution and was also synthesized with different alkylamines at its interlayer space, alternating short and long chains. Magadiite was converted in its acid form by two different methods: ion exchange with NH4+ and themolysis or by ion exchange with HCl. The diffractograms collected in crescent temperatures show that thermal stability of magadiite does not change after introduction of aluminum. The acidity of materials was measured by monitoring the CO adsorption with FTIR and the results shows that the acidity is high, comparable to zeolites. The comparison between the two different acid materials shows that the one produced by desamoniation has acid sites more accessible to probe molecules in respect to the one produced by exchange with HCl. AlPO-kanemite was used to produce polymeric composites by two methods: melt intercalation and in situ polymerization. In the first case the polymers (PP and EVA) were not able to access the interlayer space while at the second one the PS and PA6 were found in theinterlayer space, but their concentration depends on the quantities of the amines present at the material. The molecular mass of PS was not altered by the presence of the AlPO-kan but the PA6 is drastically reduced. The introduction of the metals has effect at thermal decomposition of the polymers, producing a larger quantity of a carbonaceous material when compared to its analogous, but without metals, that diminishes the flammability of the polymer. / Doutorado / Quimica Inorganica / Doutor em Ciências

Orientador: Florencia Cecilia Menegalli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-09T22:30:18Z (GMT). No. of bitstreams: 1 Guerreiro_LizielleMariaRicardo_D.pdf: 3811056 bytes, checksum: fd1a806ffefe0aee5c570c2387c47081 (MD5) Previous issue date: 2008 / Resumo: Produtos elaborados, como molhos para salada, conservas, sobremesas, pratos prontos, dentre outros, passam por bombeamento, esterilização, congelamento, ou acidificação, durante o processamento. Um ingrediente amplamente empregado nestes alimentos é o amido. Para resistir a estas condições de processo, os amidos devem conservar suas propriedades funcionais como a textura inicial, não liberar água nem alterar cor, preservar aromas, resistir a pH baixo e esterilização e aumentar a ¿vida de prateleira¿ do produto. Nem sempre o amido nativo mantém as propriedades funcionais sob condições de processo e a indústria utiliza, então, o amido modificado. Porém, a mistura de amidos poderia ser uma alternativa. Nesse contexto, os amidos de amaranto e de mandioca, a mistura dos amidos de amaranto e de mandioca, numa proporção de 1:1 e os amidos comerciais ¿Novation¿ 9460 e 9560 foram estudados, numa concentração de 5% (p/v), em pH natural e ácido de 3,5, com ou sem tratamento térmico realizado em autoclave a 121oC por 30 minutos. Os géis foram avaliados por microscopia, pelas propriedades funcionais (sinérese e vida de prateleira) e reologia. A mistura apresentou menor inchamento do que os amidos em separado. A acidez diminuiu o inchamento dos grânulos dos amidos de amaranto e mandioca, mas não influenciou o comportamento dos amidos comerciais. A gelatinização no reômetro foi influenciada pela acidez que aumentou os valores do módulo elástico para a mandioca, amaranto, mistura e 9560. As análises de gelatinização realizadas no DSC mostraram que a acidez diminuiu as temperaturas de início dos amidos de amaranto e de mandioca e aumentou a temperatura de pico do amido de amaranto. Todos os géis dos amidos com pH natural, ácido e natural autoclavado apresentaram tixotropia e comportamento pseudoplástico. O comportamento dos géis naturais de amaranto e da mistura foi modelado pela equação de Herschel-Bulkley; enquanto que o comportamento dos géis naturais de mandioca, 9460 e 9560 foi modelado pela equação de Lei da Potência. Os géis, em meio ácido, tiveram o comportamento melhor descrito pela equação de HB, com exceção do gel do amido 9560, que apresentou comportamento melhor descrito pela Lei da Potência. Para os géis autoclavados em pH natural, o comportamento foi descrito pela equação de HB e, em meio ácido, pela equação Lei da Potência, com valores de n próximos da unidade. De maneira geral, em ensaios estacionários, o gel da mistura apresentou comportamento mais próximo ao do gel de mandioca, embora em ensaios dinâmicos tenha apresentado comportamento mais próximo do gel de amaranto. Em ensaios dinâmicos, os géis natural, ácido e natural autoclavado apresentaram comportamento de gel fraco, com exceção do gel de mandioca natural autoclavado, que apresentou comportamento de suspensão. Os géis ácidos autoclavados dos amidos de amaranto, de mandioca e da mistura não apresentaram comportamento viscoelástico. Os géis de amaranto, de mandioca e da mistura apresentaram comportamento descrito pela equação de Ahrrenius, que estabeleceu uma relação de dependência da viscosidade aparente com a temperatura, independente da acidez. Para a análise de ¿vida de prateleira¿, os géis de amaranto e dos amidos comerciais apresentaram as menores variações dos valores das curvas de G¿ e G¿ durante o armazenamento / Abstract: Starch has been widely used as a thickener, stabilizer or gelling ingredients in the food like soups, sauces, snacks, canned and refrigerated food products. In this foods processing, starch dispersion are often heated, cooled and pumping at a wide range of shear rate. In many foods, sours substances (various acids) are added to foods as acidulents or preservatives. Important factors like texture, pasting properties, appearance and viscosity of starch pastes must be conserved when the starches are submit to stress conditions. But native starches present limitations that reduce their usefulness. A less costly alternative to modifications is the use of blends of native starches from different sources, which is keeping with current preferences for ¿natural¿ products. Our objective is to investigate how acidity and heat treatment effects the granules and the rheological properties of starch blends (amaranth:cassava), amaranth and cassava starch pastes. The starch gels (5%w/v), natural and acid pH, with or without heat treatment (autoclaved 121oC/30 min.) are studies through microscopy, functional properties and rheological behavior. The blend of starch showed lower swelling than pure starches. The acidity decreased swelling of the amaranth and cassava starches, but did not influence the commercials starch. The gelatinization study by rheometer was influenced by acid that increased the elastic modulus of cassava, amaranth, blend and 9560 starch gels. The gelatinization study by DSC exhibited acid influence in the initial and peak temperatures of amaranth and cassava starches. The natural, acid and natural autoclaved gels exhibited tixotropy and pseudoplastic behavior. The natural gel rheological behavior of amaranth and blend were described by HB model, although gel behaviors of cassava, 9460 e 9560 were described by Law power model. Acid gel rheological behaviors were described by HB model, except 9560 gel, that exhibited Law Power model. Natural autoclaved gels exhibit a rheological behavior were described by HB model and acid autoclaved gels were described by Law Power with n values approximately 1. A general way, in the steady test, the blend gel behavior was similar to cassava starch gels. In dynamic test, the blend behavior was similar to amaranth gels. In dynamic test, natural, acid and autoclaved natural gels were classified like weak gels, except natural autoclaved cassava gel, that exhibit behavior like entanglement suspension. Autoclaved acid of amaranth, cassava and blend did not exhibit viscoelastic behavior. The acidity influenced the n e k values parameters to different temperature. The amaranth and commercials starch gels exhibited lower changes in elastic and viscous modulus during storage / Doutorado / Doutor em Engenharia de Alimentos

Foram analisadas 72 amostras de leite humano cru recebidas do Banco de Leite do Conjunto Hospitalar de Sorocaba, com valores de acidez conhecidos. Quarenta e oito delas tinham acidez aceitável (até 8º D) e outras 24 amostras com acidez acima desse limite. Foram realizadas contagens bacterianas: bactérias lácticas, lipolíticas, coliformes totais e fecais, microrganismos aeróbios mesófilos totais e Staphylococcus coagulase positiva. Quarenta e nove questionários de freqüência alimentar foram aplicados em lactantes doadoras de leite com o propósito de estabelecer correlação entre microbiologia, acidez e nutrição das lactantes. Nas amostras com valor de acidez < 8°D as populações microbianas encontradas foram: para o grupo dos microrganismos mesófilos aeróbios totais e bactérias lácticas a população máxima encontrada ficou na ordem de 106 UFC/mL. Já para bactérias lipolíticas este valor não ultrapassou 1,9x105UFC/mL. Os coliformes totais foram isolados em 47,2% (34 amostras) das amostras analisadas, destas 87,5% confirmaram também a presença de E.coli. Para Staphylococcus coagulase positiva o valor máximo encontrado foi 1x104 UFC/mL e foi similar às amostras ácidas e não ácidas. Nas amostras rejeitadas (acidez > 8ºD) as contagens máximas tanto para o grupo de mesófilos como de bactérias lácticas foram da ordem 107 UFC/mL. As bactérias lipolíticas foram encontradas em 53,52% (13 amostras) do total de amostras analisadas e o grupo dos coliformes foi detectado em 52,94% das amostras ácidas, destas 33,33% apresentaram crescimento de E. coli. Os dados foram avaliados pela correlação de Pearson entre as variáveis: população de microrganismos mesófilos aeróbios totais e acidez Dornic. O nível de significância foi estabelecido em p<0,05. Os valores de acidez Dornic não mostraram correlação (R = 0,215) estatisticamente significativa com a população de microrganismos mesófilos aeróbios totais (UFC/mL) para as amostras analisadas. De acordo os dados nutricionais, pequenas diferenças são observadas em relação ao consumo de alimentos e alteração de acidez do leite humano. Pelos valores encontrados não foi possível detectar correlação entre a nutrição da lactante e os valores de acidez encontrados nas amostras de leite humano. / Seventy two samples of human breastmilk obtained from the Milk of the Hospitals Group of Sorocaba were analyzed, prior to pasteurization. Dornic acidity was titrated in duplicate for each sample. Forty eight of them had acceptable acidity (up to 8° D) and other 24 samples with acidity above of that limit. Quantifying the initial population: lactic bacteria, lipolitics bacteria, total coliforms and Escherichia coli, aerobic mesofilic microorganisms and Staphylococcus positive coagulase. Forty nine questionnaires of alimentary frequency were applied in lactic donors of milk with the purpose of to detect correlation among microbiology, acidity and nutrition of the lactic ones. The samples with value of acidity <8°D the found populations of microorganism were: group of the microorganisms mesofilic total aerobic and lactic bacteria the found maximum population was 106 CFU/mL. Although for lipolitics bacteria this value did not cross 1,9x105 CFU/mL. The group of total coliforms were isolated in 47,2% (34 samples) of the analyzed samples, of these 87,5% they also confirmed the presence of E.coli. In Staphylococcus positive coagulase the detect maximum value was 1x104 CFU/mL and it was similar to the acid samples and no acid. In the samples with acidity above 8ºD (rejected) the maximum population so much for the mesofilic group as of lactic bacteria they were 107 CFU/mL. The lipolitics bacteria were found in 53,52% (13 samples) of the total of analyzed samples and the group of the coliforms was detected in 52,94% of the acid samples, of these 33,33% they presented growth of E. coli. Data were analyzed to detect correlation between variables: population of aerobic mesofilic microorganisms and acidity Dornic, using Pearson`s coefficient. The level of significance was set at p <0,05. The values of acidity Dornic did not show correlation (R = 0,215) statistically significant with the population of aerobic mesofilic microorganisms (CFU/mL) for the analyzed samples. According to the data nutritional, small differences are noticed regarding to the consumption of foods and alteration of acidity of the human milk. For the found values it was not possible to detect correlation between the nutrition of the lactic and the values of acidity found in the samples of human milk.

Chez la banane dessert, les saveurs sucrée et acide, caractéristiques importantes pour les consommateurs, sont pilotées par les teneurs en acides citrique et malique. Ce travail a donc porté sur l’étude des processus physiologiques qui pilotent l’accumulation de ces acides dans la pulpe de banane (Musa sp. AA) en combinant analyse expérimentale et modélisation écophysiologique. Nous nous sommes notamment intéressés à l’effet du génotype et des conditions de croissance du fruit en adoptant une approche intégrative liant les phases pré et post récolte.Les effets de la charge en fruit, de la fertilisation potassique, et du stade de récolte sur l’accumulation du citrate et du malate dans la pulpe ont été étudiés expérimentalement. La variabilité génotypique a été prise en compte en choisissant trois génotypes présentant des acidités contrastées à maturité. Des différences d’évolution des teneurs en acides, dues à des modifications métaboliques, ont été observées entre les génotypes pendant les phases pré et post récolte. Le stade de récolte a eu un effet significatif sur les teneurs en acides des fruits pendant la maturation post récolte. La charge en fruit et la fertilisation potassique n’en ont eu aucun. Des modèles écophysiologiques ont été développés pour prédire différents critères d’acidité de la banane en pré et post récolte. Le pH et l’acidité titrable ont été prédits par un modèle d’équilibres acido-basiques, la teneur en malate par un modèle de stockage vacuolaire, et la teneur en citrate par un modèle du cycle de Krebs. Ces modèles ont permis d’identifier les processus physiologiques clés qui pilotent l’acidité de la banane. Des paramètres génotypiques ont été identifiés liés à l’activité de l’enzyme malique mitochondriale et à celle des transporteurs mitochondriaux du malate pour le modèle citrate, et à l’activité des pompes à protons vacuolaire ATPases pour le modèle malate. Ces modèles ont également permis de disséquer l’effet des conditions de croissance du fruit sur l’acidité de la banane. L’intégration des modèles développés dans un modèle d’élaboration de l’acidité et son utilisation potentielle pour l’amélioration variétale sont discutées. / Citric and malic acids determine the sourness and sweetness of banana pulp, which are the two main determinants of consumer preferences. The present work focused on the physiological processes controlling the accumulation of citric and malic acids in banana pulp (Musa sp. AA) using experimental analysis and ecophysiological modeling. We chose an integrative approach linking the pre and post-harvest stages, and focused on the effect of genotype and fruit growing conditions. Experiments were conducted to study the effect of fruit load, potassium fertilization and fruit age at harvest on the accumulation of citrate and malate in banana pulp. To account for genotypic variability, three genotypes with contrasting acidity at the eating stage were studied. Major differences in the pattern of citrate and malate accumulation were found in the three cultivars both during growth and post-harvest ripening and were shown to be the result of metabolic changes. The harvest stage had a significant effect on the concentrations of acids during post-harvest ripening. Fruit load and potassium fertilization had no effect.Ecophysiological models were developed to predict several banana acidity criteria during the pre and post harvest stages. pH and titratable acidity were predicted by a model of acid-base reactions; malate content by a model of vacuolar storage; and citrate content by a model of the TCA cycle. These models led to the identification of the key physiological processes that control banana acidity. Genotypic parameters were identified, which were related to the activity of the mitochondrial malic enzyme and of the malate mitochondrial carriers in the citrate model, as well as to the activity of the vacuolar proton pump, ATPase, in the malate model. The two models were also used to analyze the effects of fruit growth conditions on banana acidity.Combining the three models in a global model of banana acidity, and the possible use of this model for varietal improvement are discussed.

The marula tree has already become a very important alternative crop in South Africa with a great potential for further improvement. There are, however, no accurate records that have been reported on the fruit yield and quality of marula tree in Southern Africa. To utilise the fruit fully, to make proper selections from the wild trees and to develop new selections/cultivars, there is a need to have information on yield potential and fruit quality aspects. The overall objective was to determine the yield potential and to evaluate the fruit quality of different marula selections putting more emphasis on fruit quality parameters such as the fruit mass, size, total soluble solids (TSS), acidity and juice content. Four marula selections were identified during their peak production season(2004/2005/2006/2007) at Schoeman Boerdery (Orchard) between Marble-Hall and Groblersdal in Mpumalanga Province (South Africa). From each of the selections, namely; Pharulani, Toularula and Swarula, five trees were selected randomly and marked, while from the Wild marula only four trees were selected and marked. For the purpose of experimental design, the four selections were regarded as four treatments, and the marked trees per selection as the replicates. All selected trees were more or less the same in size and were in full production. The trees were growing in an orchard with planting distance of 9 m (interspacing) and 4.5 m (intraspacing). To determine yield potential, the number of fruit per square meter per tree was counted on pre-labelled branches on five positions around the tree canopy at three stages of fruit development. Collected data were converted to grams of fruit per square metre. Tree canopy size (CS), expressed as m2, was calculated by using the radius (r) of each canopy in the following formula: CS= (╥.r2) 4. For calculating the yield per tree, the average canopy size was multiplied by the number of fruit counted per m2. Twenty fruits from each labelled marula tree per selection were randomly selected; collected and taken to the Ecophysiology Laboratory at University of Pretoria for fruit quality traits, weight (mass), size, stone mass, peel mass, juice content, Total Soluble Solids (TSS) and Titratable acidity (TA). The yield efficiency/potential for both tree unit and hectare (ha) basis in 2006/2007 season, showed that the Swarula selection had the highest total yield as compared to other selections. Results showed that there was a positive relationship between fruit weight and size, that is, the bigger the weight, the bigger the size and the opposite. Generally, three selections, Swarula, Toularula and Pharulani had a higher fruit mass and size than “wild” marula. Pharulani had the highest seed/stone mass whereas “wild” marula had the lowest seed mass during the 2004/2005 and 2005/2006 fruiting seasons. Pharulani selection had the highest juice mass during both seasons whereas Swarula selection had the lowest juice mass. Results also showed that ‘wild’ marula had the highest TSS/TA ratio during both seasons whereas Pharulani had the lowest TSS/TA ratio. Optimal traits were therefore found in different selections and not in the same selections as envisaged. Copyright / Dissertation (MInst Agrar)--University of Pretoria, 2009. / Plant Production and Soil Science / unrestricted

Le Réacteur Nucléaire à sel fondu à spectre rapide (Molten Salt Fast Reactor, MSFR) est un concept innovant de quatrième génération développé par le CNRS depuis 2004 et actuellement étudié dans le cadre du projet européen SAMOFAR de H2020. Le MSFR fonctionne avec un combustible nucléaire liquide constitué d’un mélange de sels fluorures LiF-ThF₄-(UF₄/UF₃) (77,5-20-2,5) mol% fondus à haute température (700-900°C). Ce réacteur est particulièrement intéressant pour le cycle de combustible du thorium (²³²Th-²³³U). Ce concept propose un retraitement intégré du combustible nucléaire basé sur des méthodes pyrochimiques afin d’extraire la matière fissile et de séparer les actinides des produits de fission.Un schéma de traitement du sel combustible, proposé lors d’un précédent projet européen (EVOL, FP7), est basé sur les propriétés redox et acido-basiques des éléments produits par les réactions de fission et de capture ayant lieu dans le cœur du réacteur. La base d’évaluation de ce schéma a été dans un premier temps thermodynamique. Une validation expérimentale est actuellement en cours qui consiste à étudier le comportement chimique et électrochimique du sel fondu et des éléments qui y sont solubilisés. Les études précédentes sur les réacteurs sels fondus ne peuvent être utilisées que partiellement pour ce concept car la composition du sel du MSFR définie par le projet européen EVOL est différente en nature et composition des sels proposés jusqu’à présent pour ce type de réacteurs. Or, les coefficients de diffusion et d’activité dépendent des propriétés physico-chimiques du sel fondu (en particulier de la solvatation) et nous avons, lors d’études précédentes, montré que les propriétés de solvatation des sels fondus dépendent fortement de leur nature et de leur composition.Les objectifs de ce travail de thèse sont l’étude du mélange fondu LiF-ThF₄ et du comportement électrochimique de l’uranium et de l’iode dans ce mélange.L’étude électrochimique du comportement de l’uranium a montré la stabilité de deux espèces solubles (UF₄ et UF₃) de cet élément dans le milieu fondu et la possibilité de le réduire à l’état métallique. Ce point est d’importance car la co-existence de ces deux composés permettra de contrôler le potentiel du sel combustible dans le cœur du réacteur et de limiter les réactions de corrosion avec les matériaux de structure. Les coefficients d’activité de U(IV) et de U(III) ont été déterminés. Les valeurs obtenues montrent que la solvatation de l’uranium au degré d’oxydation (IV) par les ions fluorure est beaucoup plus importante que celle de l’uranium au degré (III), ce qui est en accord avec des observations ultérieures dans d’autres sels fluorures. Notre choix pour l’étude des produits de fission dans le sel combustible s’est porté sur l’iode. Dans le cœur du réacteur, la forme stable de l’iode est la forme halogénure soluble I- et dans le schéma général de traitement du sel combustible, il est prévu d’extraire l’iode par une étape de fluoration qui permet de produire le gaz I₂. Cette étude a montré la contribution d’une réaction chimique à l’oxydation des ions iodures en iode gazeux. Cette réaction chimique d’oxydo-réduction correspond à l’oxydation des ions iodures par l’oxygène. Cette réaction n’est expliquée que par l’existence d’un oxyfluorure de thorium soluble ThOF₂. Une efficacité d’extraction de I₂ (g) supérieure à 95 % a été obtenue par électrolyse à potentiel contrôlé. Ces électrolyses, qui simulent la fluoration, permettent de valider l’étape d’extraction de l’iode dans le schéma de traitement.Ce travail de recherche a permis d’acquérir une meilleure connaissance de la stabilité du sel et du comportement chimique et électrochimique de différents composés (U et I) dans le sel. / The Molten Salt Fast Reactor (MSFR) is an innovative concept of GEN IV developed by the CNRS since 2004. It is currently studied in the framework of the European project SAMOFAR of H2020. The MSFR operates with a liquid nuclear fuel consisting of a mixture of fluoride salts LiF-ThF₄- (UF₄ / UF₃) (77.5-20-2.5) mol% melted at high temperature (700-900° C). This reactor is particularly advantageous for the thorium fuel cycle (²³²Th-²³³U). This concept proposes an integrated reprocessing of the nuclear fuel based on pyrochemical methods in order to extract the fissile material and to separate the actinides from the fission products.A scheme for the treatment of the fuel salt, proposed in a previous European project (EVOL, FP7), is based on the redox and acido-basic properties of the elements produced by the fission and capture reactions occurring in the reactor core. The baseline for this scheme was initially thermodynamic. Experimental validation is currently under way to study the chemical and electrochemical behavior of the molten salt and the elements solubilized therein. Previous studies on molten salt reactors can only be partially used for this concept because the composition of the MSFR salt defined by the European EVOL project is different from the composition of the salts proposed up to now for this type of reactor. However, the diffusion and activity coefficients depend on the physicochemical properties of the molten salt (in particular solvation) and in previous studies we have shown that the solvation properties of molten salts are strongly dependent on their nature and their composition.The objectives of this thesis are the electrochemical characterization of the molten mixture LiF-ThF₄ and the study of the electrochemical behavior of uranium and iodine.The electrochemical study of the behavior of uranium shows the stability of two soluble species (UF₄ and UF₃) of this element in the molten medium and the possibility of its reduction to the metallic state. This point is important because the co-existence of these two compounds will make possible to control the potential of the fuel salt in the core of the reactor in order to limit the corrosion reactions with the structural materials. The activity coefficients of U (IV) and U (III) were determined. The values obtained show that the solvation of uranium to the degree of oxidation (IV) by fluoride ions is much greater than that of uranium to degree (III), which is in agreement with subsequent observations in other fluoride salts.Our choice for the study of fission products in the fuel salt has focused on iodine. In the core of the reactor, the stable form of the iodine is the soluble halide form I- and in the general scheme of treatment of the fuel salt, it is planned to extract iodine by a fluorination step in order to produce the gaseous compound I₂. The electrochemical study shows the contribution of a chemical reaction to the electrochemical oxidation of iodide ions in gaseous iodine. This redox chemical reaction corresponds to the oxidation of the iodide ions by oxygen. This reaction is explained for the existence of a soluble thorium oxifluoride ThOF₂. Extraction efficiencies of I₂ (g) greater than 95% were obtained by electrolysis at controlled potential. These electrolysis, which simulate fluorination process, make it possible to validate the method for the extraction of the iodine in the reprocessing scheme.This research has led to a better understanding of salt stability and of the chemical and electrochemical behavior of several compounds (U and I) in the molten salt.